Theoretical Mechanistic Study on Nickel-Catalyzed Cycloaddition of Azetidinone with Butadiene†

doi:10.7503/cjcu20180737

Abstract

Abstract:

Density functional theory(DFT) calculations were carried out on the nickel-catalyzed cycloaddition of 1-Boc-3-azetidinone and 2,3-dimethyl-1,3-butadiene. The calculation results indicate that the reaction occurs via an oxidative addition mechanism rather than experimentally proposed β-carbon elimination mechanism. The important elementary steps consist of the oxidative addition of C—C(=O) bond of azetidinone to Ni(PPh₃)₂, cis-diene insertion into the Ni—C(=O) bond and the reductive elimination of an eight-membered heterocyclic product. The rate-determining step is the olefin insertion with an acceptable Gibbs activation energy of 86.74 kJ/mol. In addition, the regioselectivity of olefin insertion was investigated. The olefin insertion into Ni—C(=O) bond is more favorable than that into Ni—C(sp³) bond, which agrees well with the experimental observation.

Key words: Nickel, Cycloaddition reaction, Reaction mechanism, Density functional theory

CLC Number:

O641

TrendMD:

ZHANG Xiaoying,DU Guifang,ZHU Bo,GUAN Wei. Theoretical Mechanistic Study on Nickel-Catalyzed Cycloaddition of Azetidinone with Butadiene^†[J]. Chem. J. Chinese Universities, 2019, 40(4): 770.

Figures/Tables 8

Fig.1 Ni0L2-catalyzed cycloaddition of 2,3-dimethyl-1,3-butadiene R1 and 1-Boc-3-azetidinone R2(Boc=tert-butoxycarbonyl)

Fig.2 Two mechanisms of Ni0L2-catalyzed cycloaddition of R1 with R2

Fig.3 Coordination modes and molecular orbitals of NiL2 and R2

Fig.4 Energy profiles(ΔG373.15K　0—) of the oxidative coupling and the β-carbon elimination steps

Fig.5 Energy profile(ΔG373.15K　0—) of the oxidative addition

Fig.6 Energy profiles(ΔG373.15K　0—) of the olefin insertion reaction

Fig.7 Energy profiles(ΔG373.15K　0—) of the most favorable catalytic cycle in the oxidative addition reaction mechanism

Fig.8 Important Kohn-Sham orbitals of Ni and R moieties in TS7

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